JP2011086950A - 溶液プロセスによる電解質をベースにした電解デバイス - Google Patents
溶液プロセスによる電解質をベースにした電解デバイス Download PDFInfo
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- JP2011086950A JP2011086950A JP2010272800A JP2010272800A JP2011086950A JP 2011086950 A JP2011086950 A JP 2011086950A JP 2010272800 A JP2010272800 A JP 2010272800A JP 2010272800 A JP2010272800 A JP 2010272800A JP 2011086950 A JP2011086950 A JP 2011086950A
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- Prior art keywords
- metal
- chalcogenide
- precursor
- layer
- solution
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- 239000002243 precursor Substances 0.000 claims abstract description 69
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8822—Sulfides, e.g. CuS
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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- C—CHEMISTRY; METALLURGY
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Abstract
【解決手段】本開示は、アモルファス・カルコゲニド固体活性電解層と、第一および第二金属層とを含む固体電解質デバイスに関する。アモルファス・カルコゲニド固体活性電解層は、第一金属層と第二金属層との間に配置される。アモルファス・カルコゲニド固体活性電解層は、金属カルコゲニドのヒドラジン・ベースの前駆物質の溶液を得、該溶液を基材上に塗布し、しかる後、前駆物質をアニールして該前駆物質をアモルファス金属カルコゲニドに変換することによって調製される。また、本開示は、固体電解質デバイスを作製するプロセスにも関する。
【選択図】図5
Description
1)ヒドラジン・ベースの前駆物質溶液を調製する。
2)該溶液を基材の上に塗布または堆積する。
3)前駆物質をアニールして該前駆物質をアモルファス・カルコゲニド膜に変換する。
R1R2N−NR3R4
で表され、この式のR1、R2、R3、およびR4の各々は、それぞれ独立した、水素、フェニルなどのアリール、メチルおよびエチルなどの1〜6個の炭素原子を有する直鎖または分岐アルキル、または3〜6個の炭素原子を有する環状アルキルである。最も典型的な溶剤はヒドラジンである。本開示はヒドラジンの使用に限定されるものでなく、以下に限らないが、1,1−ジメチルヒドラジンおよびメチルヒドラジンなど上記に開示したヒドラジン類似の溶剤、または、ヒドラジン類似の溶剤と、以下に限らないが、水、メタノール、エタノール、アセトニトリル、およびN,N−ジメチルホルムアミドを含む他の溶剤との混合剤などを含め、他の溶剤を使って本開示を用いることもできる。但し、例えば、ナトリウム、カリウム、および他のアルカリ金属など、特定の高反応性の金属に対しては、溶剤は無水であることが望ましい。
少なくとも一つの金属カルコゲニドと、H2S、H2Se、またはH2Teを有するアミン化合物の塩と、を接触させて金属カルコゲニドのアンモニウム・ベースの前駆物質を生成する工程であって、該アミン化合物は、式:
NR5R6R7
で表され、この式のR5、R6、およびR7の各々は、それぞれ独立した、水素、フェニルなどのアリール、メチルおよびエチルなど1〜6個の炭素原子を有する直鎖または分岐アルキル、または3〜6個の炭素原子を有する環状アルキルである、該工程と、
上記金属カルコゲニドのアンモニウム・ベースの前駆物質を、式:
R1R2N−NR3R4
で表されるヒドラジン化合物と接触させて、ヒドラジン化合物中に金属または半金属カルコゲニドのヒドラジニウム・ベースの前駆物質が含まれる溶液を生成する工程であって、この式のR1、R2、R3、およびR4の各々は、それぞれ独立した、水素、フェニルなどのアリール、メチルやエチルなどの1〜6個の炭素原子を有する直鎖または分岐アルキル、または3〜6個の炭素原子を有する環状アルキル、および随意的に、S、Se、Teなどの元素カルコゲンまたはこれらの組合せである、該工程と、
を含む。
GeS2前駆物質の膜は、スピン被覆技法と上記の溶液とを使って、清浄な熱酸化シリコン基材上に容易に堆積される。各基材は、最初に石鹸ブラシ洗浄を行い、次に、エタノール中とジクロロメタン中とで連続的に超音波洗浄し、最後にピラニア洗浄(過酸化水素:硫酸)を用い、脱イオン(DI:deionized)水でリンスして、前洗浄される。GeS2前駆物質の薄膜は、前述のGeS2溶液を基材の上に2〜3滴たらし、約10秒間ほど溶液が基材の上に拡がるのを待ち、該基材を、窒素を充満させたドライボックス中で、2000rpmで約2分間スピンすることによって形成される。
A 42.7 ±0.5 57.3 ±0.5 261 ±20
B 34.7 ±0.5 65.3 ±0.5 349 ±20
C 34.2 ±0.5 65.8 ±0.5 389 ±20
D 33.7 ±0.5 66.3 ±0.5 400 ±20
GeS2の溶液は、0.055gのGeS2(0.4mモル)を1.6mLの無水ヒドラジンに溶解して生成される(実施例1と同じ濃度)。該溶液は、この実施例では使用される前に約4週間保管される。反応および得られた溶液は、不活性雰囲気(例、窒素またはアルゴン)中に維持される。該溶液は、スピン被覆処理のため基材上に投与される過程で、0.2μmのシリンジ・フィルタを通してろ過される。
GeS2の溶液は、0.055gのGeS2(0.4mモル)を1.6mLの実施例2で使ったのと同じ無水ヒドラジンに溶解して生成される。該溶液は、使用の前に24時間保管される。Cu2Sの溶液は、5mLの無水ヒドラジン中の0.159gのCu2S(1mモル)および0.064gのS(2mモル)を約2週間攪拌して調製される。得られた黄色の溶液には、まだ少量の黒色しみが残っており、これは、溶液投与の過程で、0.2μmのシリンジ・フィルタを通してろ過して除去された。スピン被覆用の複合液が、0.4mLのGeS2溶液(0.1mモルのGeS2を含有)を0.25mLのろ過されたCu2S溶液(0.05mモルのCu2Sを含有)と(2分間)攪拌して調製された。全ての処理は、酸素および水分レベルが1ppmより低い、窒素充満のグローブ・ボックス中で行われる。
Claims (6)
- アモルファス・カルコゲニド固体活性電解層と、
第一金属層と、
第二金属層と、
を含む固体電解質デバイスであって、
前記アモルファス・カルコゲニド固体活性電解層は、前記第一金属層と第二金属層との間に配置され、前記アモルファス・カルコゲニド固体活性電解層は、金属カルコゲニドの前駆物質または半金属カルコゲニドの前駆物質の溶液を得て、
前記溶液を基材の上に塗布し、
しかる後、前記前駆物質を前駆物質が、金属カルコゲニドに分解することができるのに十分な高さの温度と十分な長さの時間で、かつ、実質的な結晶化を生じさせないのに十分な低さの温度と十分な短さの時間でアニールし、前記前駆物質を前記金属カルコゲニドまたは半金属カルコゲニドに変換することによって調製され、
柱状セル型であって、前記第一金属層と第二金属層との間に位置するビアを有する層間誘電体をさらに含み、前記アモルファス・カルコゲニド固体活性電解層は、前記層間誘電体中の前記ビアの中に配置される、前記固体電解質デバイス。 - アモルファス・カルコゲニド固体活性電解層と、
第一金属層と、
第二金属層と、
を含む固体電解質デバイスであって、
前記アモルファス・カルコゲニド固体活性電解層は、前記第一金属層と第二金属層との間に配置され、前記アモルファス・カルコゲニド固体活性電解層は、金属カルコゲニドの前駆物質または半金属カルコゲニドの前駆物質の溶液を得て、
前記溶液を基材の上に塗布し、
しかる後、前記前駆物質を前駆物質が、金属カルコゲニドに分解することができるのに十分な高さの温度と十分な長さの時間で、かつ、実質的な結晶化を生じさせないのに十分な低さの温度と十分な短さの時間でアニールし、前記前駆物質を前記金属カルコゲニドまたは半金属カルコゲニドに変換することによって調製され、
マッシュルーム・セル型であって、前記第一金属層と第二金属層との間に位置して金属導体を充填されたビアを有する層間誘電体をさらに含み、前記アモルファス・カルコゲニド固体活性電解層は、前記層間誘電体の上部に配置される、前記固体電解質デバイス。 - アモルファス・カルコゲニド固体活性電解層と、
第一金属層と、
第二金属層と、
を含む固体電解質デバイスであって、
前記アモルファス・カルコゲニド固体活性電解層は、前記第一金属層と第二金属層との間に配置され、前記アモルファス・カルコゲニド固体活性電解層は、金属カルコゲニドの前駆物質または半金属カルコゲニドの前駆物質の溶液を得て、
前記溶液を基材の上に塗布し、
しかる後、前記前駆物質を前駆物質が、金属カルコゲニドに分解することができるのに十分な高さの温度と十分な長さの時間で、かつ、実質的な結晶化を生じさせないのに十分な低さの温度と十分な短さの時間でアニールし、前記前駆物質を前記金属カルコゲニドまたは半金属カルコゲニドに変換することによって調製され、
細孔セル型であって、前記第一金属層と第二金属層との間に位置するビア有する層間誘電体をさらに含み、前記アモルファス・カルコゲニド固体活性電解層は、前記ビア中と前記層間誘電体の上部とに配置される、前記固体電解質デバイス。 - 前記アモルファス・カルコゲニド固体電解層の下部に配置された埋め込み金属導通部を有する層間誘電体をさらに含み、前記埋め込み金属導通部は前記第一金属の層を含む、請求項1−3に記載の固体電解質デバイス。
- 前記アニーリングは、50℃乃至400℃の温度で、かつ、0.2乃至6時間行われる、請求項1−4に記載の固体電解質デバイス。
- 前記溶液は、
金属カルコゲニドを、ヒドラジン化合物および随意的に余分のカルコゲンの中に直接溶解する工程、
単離された、金属カルコゲニドのヒドラジン・ベースの前駆物質と、溶剤とを接触させてこれらの溶液を形成する工程、
前記金属カルコゲニドの対応金属を、前記金属カルコゲニドの形成と溶液中への溶解とを促進するため少なくとも十分なカルコゲンを加えたヒドラジン化合物中に直接溶解する工程、
前形成されたヒドラジニウム・ベースの前駆物質を非ヒドラジン・ベースの溶剤中に溶解する工程、または
金属カルコゲニドとアミンの塩とを接触させて、前記金属カルコゲニドのアンモニウム・ベースの前駆物質を生成し、次にこれをヒドラジン化合物および随意的に元素カルコゲンと接触させる工程、
の一つによって調製される、請求項1−5に記載の固体電解質デバイス。
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JP2005051224A (ja) * | 2003-07-10 | 2005-02-24 | Internatl Business Mach Corp <Ibm> | カルコゲニド(chalcogenide)皮膜の溶液堆積 |
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ATE361530T1 (de) | 1999-02-11 | 2007-05-15 | Univ Arizona | Programmierbare mikroelektronische struktur sowie verfahren zu ihrer herstellung und programmierung |
US7109056B2 (en) * | 2001-09-20 | 2006-09-19 | Micron Technology, Inc. | Electro-and electroless plating of metal in the manufacture of PCRAM devices |
US6858482B2 (en) * | 2002-04-10 | 2005-02-22 | Micron Technology, Inc. | Method of manufacture of programmable switching circuits and memory cells employing a glass layer |
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KR100653701B1 (ko) | 2004-08-20 | 2006-12-04 | 삼성전자주식회사 | 반도체 소자의 작은 비아 구조체 형성방법 및 이를 사용한상변화 기억 소자의 제조방법 |
DE102004052647B4 (de) * | 2004-10-29 | 2009-01-02 | Qimonda Ag | Methode zur Verbesserung der thermischen Eigenschaften von Halbleiter-Speicherzellen im Herstellungsverfahren und nichtflüchtige, resistiv schaltende Speicherzelle |
TWI290369B (en) | 2005-07-08 | 2007-11-21 | Ind Tech Res Inst | Phase change memory with adjustable resistance ratio and fabricating method thereof |
KR100687750B1 (ko) * | 2005-09-07 | 2007-02-27 | 한국전자통신연구원 | 안티몬과 셀레늄 금속합금을 이용한 상변화형 메모리소자및 그 제조방법 |
US7517718B2 (en) | 2006-01-12 | 2009-04-14 | International Business Machines Corporation | Method for fabricating an inorganic nanocomposite |
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WO2004008535A1 (ja) * | 2002-07-11 | 2004-01-22 | Matsushita Electric Industrial Co., Ltd. | 不揮発性メモリおよびその製造方法 |
JP2005051224A (ja) * | 2003-07-10 | 2005-02-24 | Internatl Business Mach Corp <Ibm> | カルコゲニド(chalcogenide)皮膜の溶液堆積 |
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CN101681993A (zh) | 2010-03-24 |
US7928419B2 (en) | 2011-04-19 |
US20080314739A1 (en) | 2008-12-25 |
EP2176896B1 (en) | 2012-11-21 |
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